JP6563643B2 - Hair cosmetics - Google Patents

Description

  The present invention relates to a hair cosmetic.

  Hair damage is caused by weathering such as hair color treatment, permanent treatment, heating with a hair dryer, exposure to sunlight, and daily hair washing behavior. As a result, the good touch and beauty of the appearance of healthy hair are impaired. As a method for solving this problem, a method in which a conditioning component is left on the hair surface or its surface layer by applying a hair cosmetic is known (for example, see Patent Documents 1 to 3).

  However, since the conventional conditioning ingredients are not sufficiently durable, several techniques have been proposed in which the effects of the ingredients remaining on the hair persist even when the shampoo is repeated to some extent. For example, a hair treatment composition containing a hair treatment agent using a specific polymer (for example, see Patent Literature 4 and Patent Literature 5) and a copolymer obtained by solution polymerization of an ethylenically unsaturated monomer component. (For example, refer patent document 6), the hair hold formulation (for example, refer patent document 7) using the combination of a specific polymer is known.

  Further, among the decolorization or hair dye compositions, the oxidized two-component decoloration or hair dye composition in particular causes hair damage and causes tangling of hair and deterioration of touch during washing with water and shampooing. Furthermore, the entanglement of the hair causes the loss of gloss and the poorness of the hair after finishing. In addition, the hair after dyeing is further damaged by physical stimulation by daily hair care behavior such as heat or brushing by a dryer or a hair iron. For this reason, there is a problem that the touch due to the tangling of the hair is further deteriorated at the time of washing with water and shampoo, and the gloss and unity of the finished hair is further reduced.

  Therefore, in order to improve the effects such as the feeling when wet and after drying, its durability, and color retention, together with amino-modified silicone and highly polymerized silicone, a specific cationic polymer is allowed to coexist to improve the amount of adsorption of silicones. A technique has been proposed (Patent Document 8).

  On the other hand, by using amphoteric or cationic polymers in combination with anionic polymers, there has been proposed a decoloring or hair dye composition that improves the gloss and flexibility of the hair, and that provides a natural dyeing and sufficient fastness. (Patent Document 9).

  In addition, a conditioning composition containing a cationic surfactant, an anionic or amphoteric polymer, and a cationic polymer as an optional component has been proposed (Patent Document 10). The document includes polyacrylic acid (paragraph [0051]) as an example of an anionic polymer, dimethyldiallyl ammonium chloride homopolymer as a preferred cationic polymer, and a copolymer of acrylamide and dimethyldiallyl ammonium chloride (paragraph [0079]). Is listed.

JP 2004-323423 A Special table 2008-543949 JP 2006-282674 A JP 2005-36014 A Japanese Patent Laid-Open No. 10-95714 JP 2012-136464 A Special table 2009-504661 JP 2008-290953 Japanese Patent Laid-Open No. 2002-193772 Special table 2008-546806

  In any of the techniques of Patent Documents 4 to 7, the effect of improving the appearance and feel of damaged hair like a healthy hair is insufficient, and in particular, the effect of improving the fingering property of wet hair is considered. Not. In addition, although a conditioning agent is added to the two-component decolorization or hair dye composition, most of these additives are washed away by the hair washing and rinsing after the treatment, and the residual amount on the hair is reduced. These effects were not satisfactory because they were reduced. Furthermore, the technique of Patent Document 8 is not sufficiently satisfactory because of the limited sustainability of the effect, and Patent Documents 9 and 10 do not describe the sustainability of the effect at all.

  Therefore, the present invention can improve the feel and appearance of damaged hair like a healthy hair, and in particular, can improve the fingering property of wet hair and the unity of dry hair, and their effects can be improved. The present invention relates to a hair cosmetic that can be sustained without being damaged even by repeated hair washing.

  The present inventors have found that the above-described problems can be solved at a time by including a specific cationic polymer and a specific anionic polymer in the hair cosmetic.

The present invention provides a hair cosmetic containing the following components (A) and (B).
(A) Cationic polymer having a charge density of 5.0 meq / g or more and 7.0 meq / g or less
(B) Anionic polymer represented by the general formula (1) and having a viscosity of 4.0 to 40.0 mPa · s at 20 ° C. in a 4% by mass aqueous solution

[In the formula, at least one of R ¹ and R ² represents —COO ⁻ , and the remainder represents a hydrogen atom, R ³ represents a hydrogen atom or —CH ₂ COO ⁻ , l is 1.3 or more and 10 or less, and m + n is 90 or more. 98.7 or less, l + n + m is 100. ]

  The hair cosmetic composition of the present invention can improve the feel and appearance of damaged hair like a healthy hair, and in particular can improve the fingering property of wet hair and the unity of dry hair. The effect can be maintained without loss even by repeated shampooing.

  In the present specification, when the hair cosmetic is a decoloring or hair dye composition, the first agent refers to a composition containing an alkaline agent, and the second agent refers to a composition containing hydrogen peroxide. The third agent refers to a composition containing an alkaline agent and other active ingredients other than hydrogen peroxide. Furthermore, the content of “in the decoloring or hair dye composition” for each component refers to the content of “in the decoloring or hair dye composition” in the case of one agent type, and “ The content of “in the mixture of the first agent and the second agent” is indicated, and in the case of the three-agent type, the content of “in the mixture consisting of the first agent to the third agent” is indicated.

<Component (A): Cationic polymer having a charge density of 5.0 meq / g to 7.0 meq / g>
The hair cosmetic composition of the present invention contains a cationic polymer having a charge density of 5.0 meq / g or more and 7.0 meq / g or less. Here, the charge density in the cationic polymer refers to the number of moles of cationic groups per gram of polymer × 1000 (meq / g).

  The charge density of component (A) is preferably not less than 5.2 meq / g, more preferably not less than 5.5 meq / g, and more preferably not less than 5.5 meq / g, from the viewpoint of finger-holding durability of wet hair and durability of dry hair mass. Preferably it is 5.8 meq / g or more, more preferably 6.0 meq / g or more, and from the viewpoint of obtaining a good feel, it is preferably 6.5 meq / g or less.

  Examples of the component (A) include a polymer containing a diallyl quaternary ammonium salt as a constituent unit, a quaternized polyvinyl imidazolium derivative, and the like.

  As the polymer containing a diallyl quaternary ammonium salt as a structural unit, a polymer having a skeleton represented by the following general formula (2) or (3) is preferable.

[In the formula, R ⁴ and R ⁵ may be the same or different, and are a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group (such as a phenyl group), a hydroxyalkyl group, an amidoalkyl group, a cyanoalkyl group, an alkoxy group. Represents an alkyl group or a carboalkoxyalkyl group, R ⁶ and R ⁷ may be the same or different, each represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a phenyl group, and X ⁻ represents an anion (chloride ion, Bromide ion, iodide ion, sulfate anion, sulfonate anion, methyl sulfate anion, phosphate anion, nitrate anion, etc.). ]

  The polymer of diallyl quaternary ammonium salt is represented by the formula (2) or (3) from the viewpoints of sustainability of wet hair as a finger and comb, and dry hair texture and gloss. The constituent unit is preferably contained in a molecule in an amount of 65 to 100 mol%, more preferably 75 to 100 mol%, still more preferably 90 to 100 mol%, still more preferably 95 to 100 mol%.

  Specific examples of the polymer containing a diallyl quaternary ammonium salt as a structural unit include those represented by the following general formula (4) or (5).

[Wherein R ⁴ , R ⁵ and X ⁻ represent the same meaning as described above. p, q and r represent molar ratios, and p + q + r = 100. ]

  p is preferably 0-50, more preferably 0-25, still more preferably 0-10, still more preferably 0-5, and q is preferably 50-100, more preferably 65-100, still more preferably 75. -100, more preferably 90-100, more preferably 95-100, r is preferably 0-50, more preferably 0-25, still more preferably 0-10, still more preferably 0-5.

  Among these, a homopolymer of diallyl quaternary ammonium salt and a copolymer of diallyl quaternary ammonium salt and acrylic acid are preferable. Specific examples of homopolymers of diallyl quaternary ammonium salts include Marquat 100 (manufactured by Lubrizol Advanced Materials, Inc., charge density 6.2 meq / g, weight average molecular weight 150,000), diallyl quaternary ammonium salts and acrylic acid As specific examples of the copolymer, Marcoat 295 (manufactured by Lubrizol Advanced Materials, Inc., charge density 6.0 meq / g, weight average molecular weight 190,000), Marquat 280 (manufactured by Lubrizol Advanced Materials, Inc., charge density 5.0 meq / g) , Weight average molecular weight 450,000) and the like.

  As the quaternized polyvinyl imidazolium derivative, for example, a compound represented by the following general formula (6) is preferable.

[Wherein, R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and Y ⁻ represents a chloride ion, bromide ion, iodide ion, sulfate anion, sulfonate anion, or alkyl sulfate anion having 1 to 4 carbon atoms. , Phosphate anions, nitrate anions and the like, and s and t are molar ratios, and s + t = 100. ]

  T, which is the molar ratio of the monomer exhibiting cationic property, is preferably 73 or more, more preferably from the viewpoints of sustainability of fingering and combing of wet hair, and sustainability of dry hair unity and gloss. 90 or more, more preferably 93 or more, and preferably 99 or less.

  Specific examples of such quaternized polyvinyl imidazolium derivatives include a copolymer of vinylpyrrolidone and methylvinylimidazolium chloride (rubicut excellence (BASF, charge density 6.1 meq / g, weight average molecular weight 40,000)), etc. Is mentioned.

The weight average molecular weight of the component (A) is preferably 10,000 or more, more preferably 50,000 or more, from the viewpoint of the persistence of the wet hair as a finger and comb, and the dryness of the hair and the glossiness. More preferably, it is 100,000 or more, and from the viewpoint of obtaining a good feel, it is preferably 3,000,000 or less, more preferably 1,000,000 or less, and still more preferably 800,000 or less.
Here, the weight average molecular weight can be measured under the following conditions, for example, by gel permeation chromatography (GPC).
Moving bed: 50 mM LiBr, 1% CH ₃ COOH / ethanol: water = 3: 7
Column: TSK gel α-M (two in series)
Reference material: Polyethylene glycol

  Among these components (A), a homopolymer of diallyl quaternary ammonium salt or a copolymer of diallyl quaternary ammonium salt and acrylic acid is preferable.

  When the hair cosmetic is a two-component or three-component decoloring or hair dye composition, the component (A) may be contained in any of the first agent, the second agent, and the third agent, It is preferable to be contained in the first agent.

  The content of the component (A) in the hair cosmetic is preferably 0.01% by mass or more from the viewpoint of the durability of finger hair and combing of wet hair, and the durability of the unity and glossiness of dry hair. More preferably 0.1% by mass or more, further preferably 0.3% by mass or more, further preferably 0.5% by mass or more, and preferably 20% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass or less. More preferably, it is 3 mass% or less, More preferably, it is 2.5 mass% or less, More preferably, it is 2 mass% or less, More preferably, it is 1.2 mass% or less.

<Component (B): Anionic polymer of specific viscosity represented by general formula (1)>
The hair cosmetic composition of the present invention contains an anionic polymer represented by the general formula (1) and having a 4% by mass aqueous solution having a viscosity at 20 ° C. of 4.0 mPa · s to 40.0 mPa · s.

[In the formula, at least one of R ¹ and R ² represents —COO ⁻ , and the remainder represents a hydrogen atom, R ³ represents a hydrogen atom or —CH ₂ COO ⁻ , l is 1.3 or more and 10 or less, and m + n is 90 or more. 98.7 or less, l + n + m is 100. ]

  In the general formula (1), l is preferably 1.4 or more, more preferably 1.5 or more, from the viewpoint of sustainability of finger-and-comb-wetting of wet hair, and persistence of dry hair unity and gloss. More preferably, it is 3 or more, More preferably, it is 4 or more, More preferably, it is 5 or more, Preferably it is 9.5 or less, More preferably, it is 9 or less, More preferably, it is 8 or less, More preferably, it is 7.5 or less. M + n in the general formula (1) is preferably not less than 90.5, more preferably not less than 91, from the viewpoint of sustainability of wet hair as a finger and comb, and dry hair texture and gloss. More preferably, it is 92 or more, More preferably, it is 92.5 or more, Preferably it is 98.6 or less, More preferably, it is 98.5 or less, More preferably, it is 97 or less, More preferably, it is 96 or less, More preferably, it is 95 or less. In the general formula (1), m is preferably 85 or more, more preferably 88 or more, from the viewpoint of the sustainability of wet hair fingers and combs, and the dryness of the hair unit and glossiness. More preferably, it is 90 or more, preferably 98.7 or less, more preferably 97 or less, and still more preferably 96 or less. In the general formula (1), n is preferably 10 or less, more preferably 8 or less, from the viewpoints of sustainability of wet hair as a finger and comb, and dry hair texture and gloss. More preferably, it is 5 or less, More preferably, it is 2 or less. Component (B) may be a random copolymer or a block copolymer.

  The viscosity at 20 ° C. of the 4% by weight aqueous solution of component (B) is preferably 4.5 mPa · from the viewpoint of the sustainability of fingering and combing of wet hair and the unity and glossiness of dry hair. s or more, more preferably 5.0 mPa · s or more, more preferably 5.5 mPa · s or more, and from the viewpoint of obtaining a good feel, preferably 38.0 mPa · s or less, more preferably 36.0 mPa · s or less, More preferably, it is 34.0 mPa · s or less, more preferably 32.0 mPa · s or less, and further preferably 31.5 mPa · s or less. In the present invention, the viscosity of component (B) is measured according to the following method.

  The viscosity of component (B) was measured according to JIS-K6726-1994. Specifically, as the sample collection amount (S), three anionic polymers 12 g were accurately weighed to the order of 1 mg and placed in a 500 mL stoppered Erlenmeyer flask. Water (W) measured so that the predetermined concentration (Cs) of the solution was 3.8% by mass, 4.0% by mass and 4.2% by mass using the following formula (2) was added to each Erlenmeyer flask.

W = [[S × (100−R)] / Cs] −S (2)
W: amount of water added (g), S: sampled amount (g),
R: Volatile content (mass%) in the sample, Cs: predetermined concentration (mass%) of the solution

The sample is then dissolved by heating at 90 ° C. for 1 hour with stirring. This is allowed to cool to near 20 ° C and completely degassed. After defoaming, the viscosity at 20 ° C. is measured using a Brookfield type rotational viscometer with rotor No. 1 and a rotational speed of 60 revolutions. Thereafter, the horizontal axis represents the concentration and the vertical axis represents the viscosity, and a relationship graph was prepared. The viscosity (mPa · s) at a concentration of 4% by mass was obtained to one decimal place.
The volatile content (R) of the sample of the above formula (2) is calculated by the following method. The pre-washed scale bottle is dried in a constant temperature dryer at 105 ± 2 ° C. for 1 hour or more, then allowed to cool to room temperature in a desiccator, and the mass is accurately measured to the order of 1 mg. Next, weigh approximately 5 g of the sample correctly into a weighing bottle down to the order of 1 mg and dry at 105 ± 2 ° C. for 3 hours. After that, the scale bottle is taken out from the dryer and allowed to cool to room temperature in a desiccator, and the weight of the scale bottle is accurately measured to the order of 1 mg. The volatile content of the sample is calculated from the following equation (3). Obtain the result to 2 decimal places.

R = {(W ₁ −W ₂ ) / (W ₁ −W ₃ )} × 100 (3)
R: Volatile content (% by mass), W ₁ : Sample before drying and the mass (g) of the weighing bottle,
W ₂ : Weight of the sample after drying and weighing bottle (g) W ₃ : Weight of the weighing bottle (g)

  In the case where the hair cosmetic is a decolorizing or hair dye composition, component (B) is preferably contained in the second agent in the case of a two-component system, in the case of a three-component system, from the viewpoint of stability. Is preferably contained in the second agent or the third agent, and more preferably contained in the third agent.

  The content of the component (B) in the hair cosmetic composition is preferably 0.01% by mass or more from the viewpoint of the sustainability of finger-and-comb-wetting of wet hair and the unity and glossiness of dry hair. More preferably 0.1% by mass or more, further preferably 0.3% by mass or more, further preferably 0.5% by mass or more, and preferably 20% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass or less. More preferably, it is 3 mass% or less, More preferably, it is 2 mass% or less.

  The mass ratio (A) / (B) of the component (A) to the component (B) in the hair cosmetic composition of the present invention is as follows: wet hair finger-and comb comb durability, dry hair mass and gloss From the viewpoint of persistence of feeling, it is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.3 or more, and preferably 30 or less, more preferably 15 or less, still more preferably 10 or less, still more preferably 5 Hereinafter, it is further preferably 3 or less, more preferably 2 or less, and still more preferably 1 or less. By setting it as this mass ratio, generation | occurrence | production of the precipitate by water-insoluble complex formation in hair cosmetics can be suppressed.

  When the hair cosmetic is a two-component or three-component decoloring or hair dye composition, the component (A) and the component (B) are preferably contained in different agents from the viewpoint of stability. In the case of the two-component type, it is preferable to contain the component (A) in the first agent and the component (B) in the second agent. In the case of the three-component type, the component (A) is contained in the first agent. Is preferably contained in the second agent or the third agent.

[Surfactant]
The hair cosmetic composition of the present invention can contain a surfactant. When the hair cosmetic is a two-component or three-component decoloring or hair dye composition, the surfactant may be contained in any of the first agent, the second agent, and the third agent. As the surfactant, any of an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant can be used.

  Examples of the anionic surfactant include sulfate anionic surfactants such as alkyl sulfates and alkyl ether sulfates; N-acyl amino acid salts, N-acyl-N-alkyl amino acid salts, amide type N-acyl amino acid salts Carboxylic acid anionic surfactants such as ether carboxylate, fatty acid salt, alkyl succinate or alkenyl succinate; sulfosuccinate type, isethionate type, taurine salt type, alkylbenzene sulfonate type, α- Examples thereof include sulfonic acid type anionic surfactants such as olefin sulfonate type and alkane sulfonic acid type; and phosphate ester type anionic surfactants such as alkyl phosphate and alkyl ether phosphate. Among these, a carboxylic acid type and a sulfuric acid ester type are preferable, and among these, a carboxylic acid type is preferable. Among the carboxylic acid-based anionic surfactants, N-acyl amino acid salts and ether carboxylates are preferable, and among them, the acyl group has 10 to 18 carbon atoms, preferably 10 to 16 carbon atoms, and more preferably 10 to 14 N- Acyl glutamate, alkyl group having 10 to 18, preferably 10 to 16, more preferably 10 to 14 carbon atoms, and an average added mole number of oxyethylene group of 3 to 15, preferably 3 to 12, more preferably 4 to 10 Of these, polyoxyethylene alkylcarboxylates are preferred.

  Nonionic surfactants include alkyl polyglucosides, polyoxyalkylene alkyl ethers, alkyl glyceryl ethers and the like. As the alkyl polyglucoside, those in which the alkyl group has 8 to 18 carbon atoms, more preferably 8 to 14 carbon atoms, and further 9 to 11 carbon atoms are preferable, and those in which the alkyl group is linear are preferable. The average degree of polymerization of glucoside is preferably 1 to 5, and more preferably 1 to 2. As the polyoxyalkylene alkyl ether, those in which the alkyl group has 10 to 22 carbon atoms, more preferably 12 to 18 carbon atoms, are preferred, and those in which the alkyl group is linear are preferred. Polyoxyethylene alkyl ethers are more preferable, and those having an average addition mole number of oxyethylene groups of 1 to 50, more preferably 2 to 40 are particularly preferable. As the alkyl glyceryl ether, those in which the alkyl group has 8 to 18 carbon atoms, more preferably 8 to 12 carbon atoms, are preferred, and those in which the alkyl group is branched are preferred.

  As the cationic surfactant, mono-long-chain alkyl quaternary ammonium salts and di-long-chain alkyl quaternary ammonium salts are preferable. Specifically, cetrimonium chloride, steartrimonium chloride, behentrimonium chloride, stearalkonium chloride. Benzalkonium chloride, stearoxypropyltrimonium chloride, dialkyl (C12-18) dimonium chloride, etc., steartrimonium chloride, behentrimonium chloride, stearoxypropyltrimonium chloride, dialkyl (C12-18) More preferred is dimonium chloride. Commercially available cationic surfactants include Coatamine 86W, 86P Conch, 60W, E-80K, D2345P (above, manufactured by Kao Corporation), Nikkor CA-2580 (manufactured by Nippon Surfactant Kogyo Co., Ltd.).

  Amphoteric surfactants include carbobetaines, amidebetaines, sulfobetaines, hydroxysulfobetaines, amidesulfobetaines, phosphobetaines, imidazo having 8 to 24 carbon atoms, alkyl groups, alkenyl groups or acyl groups. Examples thereof include linium-based surfactants, and among them, carbobetaine-based surfactants and sulfobetaine-based surfactants are preferable. Preferred amphoteric surfactants include lauric acid amidopropyl betaine, coconut oil fatty acid amidopropyl betaine, lauryldimethylaminoacetic acid betaine, lauryl hydroxysulfobetaine and the like.

  Two or more surfactants can be used in combination, and the content in the hair cosmetic is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably from the viewpoint of the stability of the hair cosmetics. Is 1% by mass or more, preferably 30% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass or less, and further preferably 15% by mass or less.

  When the hair cosmetic composition of the present invention is a shampoo, it preferably contains an anionic surfactant. Among them, from the viewpoint of foaming and detergency, sulfate anionic interfaces such as alkyl sulfates and alkyl ether sulfates are preferred. An activator is preferably used. The content of the anionic surfactant in the shampoo is 2% by mass or more, more preferably 2.5% by mass or more, further 3% by mass or more, and further preferably 5% by mass or more, and 30% by mass or less, and further 25%. It is preferably at most 20 mass%, more preferably at most 20 mass%, further preferably at most 15 mass%. The mass ratio of the anionic surfactant to the total of the component (A) and the component (B) (anionic surfactant / [component (A) + component (B)]) is 0.3 or more from the viewpoint of shampoo stability. Further, it is preferably 0.5 or more, more preferably 1 or more, and further preferably 1.5 or more, and is preferably 10 or less, more preferably 8 or less, further 7 or less, and even more preferably 4 or less.

  Further, when the hair cosmetic composition of the present invention is a hair rinse, a hair conditioner or a hair treatment, it preferably contains a cationic surfactant, and from the viewpoint of smoothing hair after rinsing and drying, Chain alkyl quaternary ammonium salts and dilong chain alkyl quaternary ammonium salts are preferred. The content of the cationic surfactant in the hair rinse, the hair conditioner or the hair treatment is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, further preferably 1% by mass or more, and 15% by mass or less, and further 10% by mass. % Or less, more preferably 8% by mass or less. The mass ratio of cationic surfactant to the sum of component (A) and component (B) (cationic surfactant / [component (A) + component (B)]) is the stability of hair rinse, hair conditioner or hair treatment. From the viewpoint, it is preferably 0.3 or more, more preferably 0.5 or more, and more preferably 1 or more, and is preferably 10 or less, more preferably 8 or less, further 6 or less, further 4 or less, and further 2 or less.

  Further, when the hair cosmetic composition of the present invention is a decoloring or hair dye composition, the content of the surfactant is 2% by mass or more from the viewpoint of the stability of the decoloring or hair dye composition, Is preferably 2.5% by mass or more, more preferably 3% by mass or more, 20% by mass or less, further 15% by mass or less, further 10% by mass or less, further 8% by mass or less, and further 7% by mass or less. Furthermore, 6 mass% or less is preferable.

[Higher alcohol]
The hair cosmetic composition of the present invention preferably contains a higher alcohol having 12 or more carbon atoms from the viewpoint of improving touch and stability. These have the effect of forming a structure with a surfactant to prevent separation and improving the feel during rinsing. In the case of the two-part type or the three-part type, the higher alcohol may be contained in any of the first agent, the second agent, and the third agent.

  As the higher alcohol, those having 12 or more carbon atoms, more preferably 16 or more, and 30 or less carbon atoms, and further 22 or less are preferable. Specifically, myristyl alcohol, cetyl alcohol, stearyl alcohol, aralkyl alcohol, behenyl alcohol , Isostearyl alcohol, 2-octyldodecanol, oleyl alcohol, and the like, and mixtures thereof.

  Two or more types of higher alcohols may be used in combination, and the content thereof is preferably 3% by mass or more, more preferably 4% by mass or more in the hair cosmetic from the viewpoint of the viscosity and stability of the hair cosmetic, 11 mass% or less, more preferably 9 mass% or less.

[Polyhydric alcohol]
The hair cosmetic composition of the present invention preferably further contains a polyhydric alcohol. In the case of the two-part type or the three-part type, the polyhydric alcohol may be contained in any of the first agent, the second agent, and the third agent. As the polyhydric alcohol, those having 2 to 20 carbon atoms, specifically, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1,2-butylene glycol, 1, Alkylene glycols such as 3-butylene glycol, pentylene glycol and hexylene glycol; Glycerins such as glycerin, diglycerin and polyglycerin; Sugar alcohols such as xylit, mannitol, galactit and sorbit; Other trimethylolethane, triglycerides Examples include methylolpropane and pentaerythritol.

  Two or more polyhydric alcohols may be used in combination. In addition, the content in the hair cosmetic is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 1% by mass or more from the viewpoint of imparting moisture to the hair and being excellent in the effect of suppressing hair crispness. Further, it is preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 10% by mass or less.

[Conditioning ingredients]
Moreover, the hair cosmetic composition of the present invention can contain a conditioning component selected from silicones and oils.

  Examples of silicones include polydimethylsiloxanes and modified silicones (for example, amino-modified silicone, fluorine-modified silicone, alcohol-modified silicone, polyether-modified silicone, epoxy-modified silicone, alkyl-modified silicone, and aminopolyether-modified silicone). , Cyclic polydimethylsiloxane, and highly polymerized methyl polysiloxane emulsion, especially polydimethylsiloxanes, polyether-modified silicones, amino-modified silicone, cyclic polydimethylsiloxane, aminopolyether-modified silicone, and highly polymerized methyl polysiloxane emulsions. preferable.

  These silicones can be used alone or in combination of two or more. The content of silicones is preferably 0.1% by mass or more, more preferably 0.5% by mass or more in hair cosmetics from the viewpoint of sufficient effects, and 20% by mass in hair cosmetics from the viewpoint of suppression of stickiness. Hereinafter, it is more preferably 15% by mass or less.

  Oils include hydrocarbons such as squalene, squalane, petrolatum, paraffin, liquid paraffin, liquid isoparaffin, cycloparaffin; glycerides such as castor oil, cocoa oil, mink oil, avocado oil, olive oil, shea butter; beeswax, whale wax , Lanolin, carnauba wax, etc .; isopropyl palmitate, isopropyl myristate, octyldodecyl myristate, hexyl laurate, cetyl lactate, propylene glycol monostearate, oleyl oleate, hexadecyl 2-ethylhexanoate, isononyl isononanoate, isononane Ester oil such as tridecyl acid; capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, lanolin fatty acid, iso fatty acid, anteiso fatty acid, coconut oil Acid, 18-methyleicosanoic acid, 16-methyl octadecanoic acid and higher fatty mixtures of these fatty acids / branched fatty and the like.

  These oil agents can be used alone or in combination of two or more. The content of the oil is preferably 0.1% by mass or more, more preferably 0.5% by mass or more in the hair cosmetic from the viewpoint of the touch improvement effect, and from the viewpoint of stability against separation of the hair cosmetic, Is preferably 20% by mass or less, more preferably 15% by mass or less.

  Since such a conditioning component remains in hair appropriately, a good conditioning effect can be imparted.

〔dye〕
When the hair cosmetic composition of the present invention is a hair dye composition, it contains a dye. When the hair dye composition is a one-component type, it contains a direct dye in the hair dye composition, and when it is a two-component or three-component type, it contains an oxidative dye intermediate or a direct dye in the first agent. Can be made.

(Oxidized dye intermediate)
As the oxidation dye intermediate, known precursors and couplers usually used in hair dyes can be used. Examples of the precursor include paraphenylenediamine, toluene-2,5-diamine, N-phenylparaphenylenediamine, N, N-bis (hydroxyethyl) paraphenylenediamine, 2-hydroxyethylparaphenylenediamine, paraaminophenol, and paramethyl. Examples include aminophenol, 4-amino-methcresol, orthoaminophenol, and salts thereof.

  Examples of the coupler include resorcin, 2-methylresorcin, 1-naphthol, 1,5-dihydroxynaphthalene, 5-aminoorthocresol, metaphenylenediamine, metaaminophenol, 2,4-diaminophenoxyethanol, 2,6- Examples include diaminopyridine, 2-methyl-5-hydroxyethylaminophenol, 2-amino-3-hydroxypyridine, and salts thereof.

  Two or more precursors and couplers may be used in combination, and the content of each of the precursor and the coupler is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and 5% by mass or less in the hair dye composition. Furthermore, 4 mass% or less is preferable.

(Direct dye)
Examples of direct dyes include acid dyes, nitro dyes, disperse dyes, and basic dyes. More specifically, examples of the acid dye include blue No. 1, purple No. 401, black No. 401, orange color No. 205, red No. 227, red No. 106, yellow No. 203, acidic orange 3, etc., and nitro dyes As 2-nitro-p-phenylenediamine, 2-amino-6-chloro-4-nitrophenol, 3-nitro-p-hydroxyethylaminophenol, 4-nitro-o-phenylenediamine, 4-amino-3 -Nitrophenol, 4-hydroxypropylamino-3-nitrophenol, HC blue 2, HC orange 1, HC red 1, HC yellow 2, HC yellow 4, HC yellow 5, HC red 3, N, N-bis (2 -Hydroxyethyl) -2-nitro-p-phenylenediamine and the like, and disperse dyes include disperse purple 1, disperse blue 1, disperse black 9 and the like, and basic dyes include basic blue 99, Basic tea 16, basic tea 17, basic red 76, basic yellow 76, basic orange 31, basic red 51, and the like.

  Two or more direct dyes may be used in combination, and in the case of a two-component or three-component hair dye composition, it may be used in combination with an oxidation dye intermediate. Moreover, the content is 0.001 mass% or more in a hair dye composition, Furthermore, 0.01 mass% or more is preferable, and 5 mass% or less, Furthermore, 3 mass% or less is preferable.

[Alkaline agent]
When the hair cosmetic composition of the present invention is a decolorizing or hair dye composition, an alkaline agent can be contained. When the decolorizing or hair dye composition is a two-part or three-part type, the first agent contains an alkaline agent. Alkaline agents include ammonia and salts thereof, sodium hydroxide, potassium hydroxide, monoethanolamine, isopropanolamine, 2-amino-2-methylpropanol, 2-aminobutanol and other alkanolamines and salts thereof, 1,3- Examples include alkanediamines such as propanediamine and salts thereof, and carbonates such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, and guanidine carbonate.

  Two or more alkali agents may be used in combination, and the content in the decoloring or hair dye composition is 0.05% by mass or more, more preferably 0.1% by mass or more, from the viewpoint of sufficient hair dyeing effect. 0.2 mass% or more is preferable, and 5 mass% or less, and also 3 mass% or less are preferable from the point of reduction of hair damage or scalp irritation.

〔hydrogen peroxide〕
When the decolorization or hair dye composition of the present invention is a two-part or three-part type, the second agent can contain hydrogen peroxide. The content of hydrogen peroxide in the decoloring or hair dye composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 1% by mass or more from the viewpoint of sufficient hair dyeing effect. From the viewpoint of reducing damage and scalp irritation, it is preferably 12% by mass or less, more preferably 9% by mass or less, and further preferably 6% by mass or less.

[Other optional ingredients]
In addition to the above components, other components that are usually used as cosmetic raw materials can be added to the hair cosmetic of the present invention. Such optional ingredients include thickeners, preservatives, chelating agents, stabilizers, antioxidants, plant extracts, herbal extracts, protein hydrolysates, vitamins, dyes and other coloring agents, and flavorings. , UV absorbers, pearlizing agents such as ethylene glycol difatty acid esters, set polymers, amphiphilic amide lipids, and the like.

  Polymers for setting include: Polysilicone-9; polyvinylpyrrolidone-based polymer (eg, polyvinylpyrrolidone, vinylpyrrolidone / vinyl acetate copolymer, vinylpyrrolidone / vinyl acetate / vinyl propionate terpolymer, vinylpyrrolidone / alkylamino Acrylate (quaternary chloride) copolymer, vinyl pyrrolidone / acrylate / (meth) acrylic acid copolymer, vinyl pyrrolidone / alkylamino acrylate / vinyl caprolactam copolymer, etc.); methyl vinyl ether / alkyl maleic anhydride alkyl half ester copolymer Polymer; acidic polyvinyl acetate polymer (for example, vinyl acetate / crotonic acid copolymer, vinyl acetate / crotonic acid / vinyl neodecanoate copolymer, vinyl acetate / crotonic acid / vinyl propionate copolymer, etc.); acidic ( Me ) Acrylic polymer (eg, (meth) acrylic acid / (meth) acrylic acid ester copolymer, acrylic acid / acrylic acid alkyl ester / alkyl acrylamide copolymer, etc.); Amphoteric acrylic polymer (eg, N-methacryloylethyl) -N, N-dimethylammonium · α-N-methylcarboxybetaine / butyl methacrylate copolymer, hydroxypropyl acrylate / butylaminoethyl methacrylate / octylamide acrylate copolymer, etc.); acrylamide / acrylate ester Copolymers; chitin / chitosan compounds (for example, hydroxypropyl chitosan, carboxymethyl chitin, carboxymethyl chitosan, etc.) and the like.

  The content of the setting polymer in the hair cosmetic is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 5% by mass or less, and further preferably 3% by mass or less. The setting polymer is more preferably used when the hair cosmetic is a styling agent.

[Medium]
In the hair cosmetic composition of the present invention, water is used as a medium. The water content in the hair cosmetic is preferably 10% by mass or more, more preferably 20% by mass or more, and further preferably 30% by mass or more, and 90% by mass or less, more preferably 80% by mass or less, and further 75% by mass. The following is preferred.

  In the hair cosmetic composition of the present invention, an organic solvent is used as necessary as a medium other than water. Examples of organic solvents include aromatic alcohols such as benzyl alcohol and benzyloxyethanol, lower alkanols such as ethanol and 2-propanol, polyols such as propylene glycol, 1,3-butanediol, diethylene glycol, and glycerin, ethyl cellosolve, Examples thereof include cellosolves such as butyl cellosolve and benzyl cellosolve, and carbitols such as ethyl carbitol and butyl carbitol.

[PH]
When the hair cosmetic composition of the present invention is other than a depigmenting agent or a hair dye composition, the pH of the hair cosmetic composition at 25 ° C. is preferably 2 or more, more preferably 4.5 or more, still more preferably 5.5 or more, It is preferably 12 or less, more preferably 11.5 or less, and still more preferably 11 or less.

  When the hair cosmetic composition of the present invention is a depigmenting agent or hair dye composition, the preferred pH of the decoloring agent or hair dye composition at 25 ° C. is as follows. In the case of a one-component hair dye composition using an acidic dye, the pH at 25 ° C. of the decolorizer or hair dye composition is preferably 1 or more, more preferably 2.5 or more, and preferably 5.5 or less, more preferably 4.5 or less. . In the case of a one-component hair dye composition using a basic dye, it is preferably 3.5 or more, more preferably 4 or more, and preferably 8 or less, more preferably 6 or less. In the case of a two-part or three-part decoloring agent or hair dye composition, the pH of the first agent (25 ° C.) is preferably 8 to 12, and the pH of the second agent (25 ° C.) is preferably 2 to 5. The pH of the mixture of the first agent and the second agent or the mixture of the first agent, the second agent and the third agent (25 ° C.) is 8 to 11.5, from the viewpoint of decolorization / hair dyeing effect and skin irritation. Furthermore, 9-11 are preferable.

  For adjusting the pH, a pH adjusting agent can be used. As a pH adjuster, as an alkaline agent, ammonia or a salt thereof; an alkanolamine such as monoethanolamine, isopropanolamine, 2-amino-2-methylpropanol, 2-aminobutanol or a salt thereof; 1,3-propanediamine, etc. Alkanediamines or salts thereof; carbonates such as guanidine carbonate, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate; hydroxides such as sodium hydroxide and potassium hydroxide can be used. In addition, as acid agents, inorganic acids such as hydrochloric acid and phosphoric acid; organic acids such as citric acid, glycolic acid and lactic acid; hydrochlorides such as monoethanolamine hydrochloride; dipotassium dihydrogen phosphate, disodium monohydrogen phosphate, etc. The phosphate etc. of this can be used.

  These pH adjusters may be used alone or in combination with an acid agent, and the content thereof is 0.01% by mass or more in hair cosmetics from the viewpoint of reducing hair damage and scalp irritation. Furthermore, 0.1 mass% or more is preferable, and 20 mass% or less in hair cosmetics, Furthermore, 15 mass% or less is preferable.

[Drug type]
The dosage form of the hair cosmetic composition of the present invention can be in the form of, for example, liquid, emulsion, cream, gel, paste, mousse or aerosol. In addition, when setting it as aerosol, content of each component described so far and pH of hair cosmetics are content in the stock solution which does not contain a propellant, and pH of stock solution.

  The hair cosmetics of the present invention are pre-shampoo treatments, shampoos, hair rinses, hair conditioners, hair treatments, after-shampoo treatments, etc .; non-aerosol foams, aerosol foams, hair gels, hair mousses, hair mists, hair lotions, hair oils, styling agents It can be suitably used for an out bath agent such as a decoloring agent or a hair dye composition.

Examples of the decolorization or hair dye composition include a one-part hair dye composition, a two-part decoloration or hair dye composition, and a three-part decoloration or hair dye composition.
The one-component hair dye composition is a composition containing a direct dye, and commonly known products include hair nail polish, acidic color, color rinse, and color treatment. Examples of the product form of the one-component hair dye composition include a gel type, a cream type, and an aerosol type.
The two-component bleaching or hair dye composition is composed of a first agent containing an alkali agent and a second agent containing hydrogen peroxide, and products commonly called hair bleach and hair color exist. Examples of the product form of the two-component decoloring or hair dye composition include a cream type, an emulsion type, a liquid type, an aerosol type, and a foam type.
In addition to the first agent and the second agent used in the above-mentioned two-component decoloring or hair dye composition, the three-component decoloring or hair dye composition further comprises an active ingredient (for example, an excessive component for improving decolorization power). It is comprised from the 3rd agent containing a sulfate (ammonium persulfate, potassium persulfate, sodium persulfate, etc.). Examples of the product form of the three-part decoloring or hair dye composition include a cream type, an emulsion type, a liquid type, an aerosol type, and a foam type as in the two-part decoloring or hair dye composition.

[Usage method (hair treatment method)]
The treatment of the hair with the hair cosmetic of the present invention is performed by bringing the hair cosmetic into contact with the hair directly or using a tool. For the method of contact, a method generally used widely in the type of hair cosmetic can be applied.For example, in the case of a pre-shampoo treatment, an appropriate amount is brought into contact with dry or wet hair before shampooing, Washing with running water after leaving it for several seconds to several tens of minutes, in the case of shampoo, touching the appropriate amount to the hair, massage for several minutes while foaming, washing with running water, hair rinse, hair conditioner, hair treatment, after shampoo treatment, etc. In the case of shampoo treatment, an appropriate amount is brought into contact with the hair, and after standing for a few seconds to several tens of minutes, washed with running water, in the case of hair mousse, hair oil, styling agent, etc., an appropriate amount is brought into contact with the hair and left as it is. . Here, the appropriate amount is an amount that is about 1: 0.005 to 1:10 in the bath ratio with respect to the mass of the hair. The hair to be treated may be all or a part thereof. The temperature when applied to the hair is preferably from room temperature to body temperature, but may be heated to about 50 ° C. to promote penetration.

  Moreover, in the case of a decoloring or hair dye composition, for example, a decoloring or hair dye composition (first agent and second agent in the case of two-agent type, and further third agent in the case of three-agent type immediately before use. After mixing) is applied to the hair, allowed to stand for a predetermined time, rinsed with water, and dried. The application temperature to the hair is preferably 15 to 45 ° C., the application time is 3 to 60 minutes, more preferably 5 to 45 minutes, and further preferably 10 to 30 minutes.

Examples 1-14, Comparative Examples 1-4
Hair cosmetics shown in Tables 1 and 2 were prepared according to a conventional method. According to the following method and criteria, the combing force was measured, the wetness of the hair was evaluated, and the dryness of the hair was evaluated.

Hair treatment method 10 g (30 cm length) of a Japanese hair bundle damaged by repeated bleaching and washing was prepared. This is the hair before treatment. For this hair, the hair cosmetics (pre-shampoo treatment composition) listed in Tables 1 and 2 are applied to the hair at a bath ratio (hair mass: aqueous solution mass) of 1: 1 respectively, and left for 5 minutes after running. Too dry. This is the hair immediately after the treatment. Further, the hair is washed and dried with the following shampoo under normal conditions 14 times. This is the hair after 14 shampoo washings.

Shampoo (mass%)
Ammonium laureth sulfate (Emar 125A, Kao) 12
Polyquaternium-10 (Caticello M-80, Kao Corporation) 0.14
Guar hydroxypropyltrimonium chloride (Jaguar C-17SK, Solvay) 0.36
Polyquaternium-7 (Marcote 550, Lubrizol Advanced Materials, Inc.) 0.18
Lauryl hydroxysultain (Amphithol 20HD, Kao) 1.7
PPG-7 (Adeka Carpole DL-30, Adeka) 1.1
Benzyl alcohol 0.3
Sodium chloride 0.1
Purified water remaining

Sensory evaluation (finger perception during rinsing)
When the hair bundle treated by the above method (immediately after treatment and after 14 shampoo washings) was rinsed with water, sensory evaluation was performed by the 10 panelists in the following five stages. The total points are shown in Tables 1 and 2.
+2: Good fingering compared to Comparative Example 1 +1: Slightly good fingering compared to Comparative Example 1 0: Compared to Comparative Example 1, fingering is almost equivalent -1: Compared to Comparative Example 1, fingering is good Slightly bad-2: Compared to Comparative Example 1, the fingering is bad

Sensory evaluation (dry hair mass)
The group of hair bundles (immediately after treatment and after 14 shampoo washings) treated by the above method (at the time of drying) was subjected to sensory evaluation in the following five stages by 10 professional panelists. The total points are shown in Tables 1 and 2.
+2: Compared with Comparative Example 1, there is no jumping hair and the unity is good +1: Compared with Comparative Example 1, the unity is slightly better 0: Compared with Comparative Example 1, the unity is almost equivalent -1: Compared with Comparative Example 1, the unity Slightly bad-2: Compared with Comparative Example 1, there are many jumping hairs and the unity is bad

Physical property evaluation (combing force during rinsing; combing force test)
In order to evaluate the physical properties, the hair bundle treated by the above method (immediately after treatment, after 14 times of shampoo washing) was hung on a force gauge immediately after rinsing with water, and then the hair tress was moved forward and backward or on both sides with two hair brushes. The combing was performed 15 times, and the force applied during each combing was measured. As the measuring apparatus, the one described in J. Soc. Cosmet. Chem. Japan. Vol. 27, No. 1, P11-13 1993 was used. Combing was performed at a rate of about 1 per second. Of the measured combing force, combing property was evaluated by the average value of the measured values (maximum value) for 10 times excluding the first 5 times. In addition, Kao Lunet (full length: about 20 cm, comb part size: about 4 × 10 cm, comb tooth density: 6 / cm) was used as the hair brush. Tables 1 and 2 show the average of 10 measurements (maximum values).

* 1: Marcote 100 (Lubrizol Advanced Materials, Inc., charge density 6.2meq / g)
* 2: Marcote 295 (Lubrizol Advanced Materials, Inc., charge density 6.0 meq / g)
* 3: Marcote 280 (Lubrizol Advanced Materials, Inc., charge density 5.0 meq / g)
* 4: Rubycut Excellence (BASF, charge density 6.1meq / g)
* 5: Marcote 550 (Lubrizol Advanced Materials, Inc., charge density 3.1meq / g)
* 6: Itaconic acid-modified polyvinyl alcohol (manufactured by Kuraray Co., Ltd., viscosity of 5.0 mPa · s at 20 ° C. in 4% by weight aqueous solution, R ¹ = −H, R ² = −COO ⁻ , R ³ = − in the formula (1) CH ₂ COO ⁻ , l = 7.5, m = 90.5, n = 2.0)
* 7: Itaconic acid-modified polyvinyl alcohol (manufactured by Kuraray Co., Ltd., viscosity of 21.5 mPa · s at 20 ° C. in a 4 mass% aqueous solution, in formula (1), R ¹ = −H, R ² = −COO ⁻ , R ³ = − CH ₂ COO ⁻ , l = 7.5, m = 90.5, n = 2.0)
* 8: Itaconic acid-modified polyvinyl alcohol (manufactured by Kuraray Co., Ltd., viscosity of 5.8 mPa · s at 20 ° C. in a 4 mass% aqueous solution, R ¹ = −H, R ² = −COO ⁻ , R ³ = − in the formula (1) CH ₂ COO ⁻ , l = 2.5, m = 95.5, n = 2.0)
* 9: Maleic acid-modified polyvinyl alcohol (manufactured by Kuraray Co., Ltd., viscosity of 31.2 mPa · s at 20 ° C. in a 4 mass% aqueous solution, in formula (1), R ¹ = −COO ⁻ , R ² = −COO ⁻ , R ³ = -H, l = 2.0, m = 96.0, n = 2.0)
* 10: Itaconic acid-modified polyvinyl alcohol (manufactured by Kuraray Co., Ltd., viscosity 3.7 mPa · s at 20 ° C. of 4 mass% aqueous solution, R ¹ = −H, R ² = −COO ⁻ , R ³ = − in the formula (1) CH ₂ COO ⁻ , l = 2.0, m = 96.0, n = 2.0)
* 11: Itaconic acid-modified polyvinyl alcohol (manufactured by Kuraray Co., Ltd., viscosity 32.2 mPa · s at 20 ° C. of 4 mass% aqueous solution, in formula (1), R ¹ = −H, R ² = −COO ⁻ , R ³ = − CH ₂ COO ⁻ , l = 1.25, m = 96.75, n = 2.00)

Formulation Example 1 (Shampoo) (mass%)
Itaconic acid-modified polyvinyl alcohol ^{* 1} 4.0
Dimethyldiallylammonium chloride / acrylic acid copolymer liquid (40% by mass) ^{* 2} 6.0
Polyoxyethylene (2) sodium lauryl ether sulfate 11.0
Polyoxypropylene (3) octyl ether 1.0
Mono 2-ethylhexyl glyceryl ether 1.0
Lauryl hydroxysulfobetaine 2.0
Polyoxyethylene (6) stearyl ether 2.0
Lauric acid 0.8
Dipotassium glycyrrhizinate 0.1
Palm oil fatty acid monoethanolamide 1.0
Lauric acid amidopropyl betaine 0.5
Dimethylpolysiloxane ^{* 3} 1.5
Amino polyether-modified silicone ^{* 4} 0.2
Ethylene glycol distearyl ester 1.5
Dipropylene glycol 3.0
Benzyloxyethanol 0.5
l-Menthol 1.0
Sodium chloride 1.0
Perfume
pH adjuster (sodium hydroxide) Amount of pH 5.0
Purified water Total remaining 100
* 1: Itaconic acid-modified polyvinyl alcohol (manufactured by Kuraray Co., Ltd., viscosity of 5.0 mPa · s at 4 ° C. in a 4% by weight aqueous solution, in formula (1), R ¹ = −H, R ² = −COO ⁻ , R ³ = − CH ₂ COO ⁻ , l = 7.5, m = 90.5, n = 2.0)
* 2: Marcote 295 (Lubrizol Advanced Materials, Inc., charge density 6.0 meq / g)
* 3: Silicone CF2450 (Toray Dow Corning)
* 4: Silicone SILSTYLE104 (Toray Dow Corning)

Formulation Example 2 (hair treatment) (mass%)
Itaconic acid-modified polyvinyl alcohol ^{* 1} 2.0
Dimethyldiallylammonium chloride / acrylic acid copolymer liquid (40% by mass) ^{* 2} 3.13
Stearic acid dimethylaminopropylamide 1.0
Behenyl alcohol 4.0
Stearyl alcohol 3.0
Benzyl alcohol 1.0
Polypropylene glycol (molecular weight 300) 1.0
Behenyltrimethylammonium chloride 1.5
Highly polymerized methylpolysiloxane ^{* 3} 2.0
Squalene 1.0
Hydroxyethyl cellulose (Mw = 500,000) 0.3
Isononyl isononanoate 1.0
Dipentaerythritol fatty acid ester ^{* 4} 0.3
Hydrolyzed casein 0.1
Aloe extract 0.1
Methylparaben 0.1
Rice germ oil 0.6
L-glutamic acid 0.5
Fragrance 0.4
Purified water Total remaining 100
* 1: Itaconic acid modified polyvinyl alcohol (manufactured by Kuraray Co., Ltd., viscosity of 5.0 mPa · s at 4 ° C. in a 4 mass% aqueous solution, R ¹ = −H, R ² = −COO ⁻ , R ³ = − in the formula (1) CH ₂ COO ⁻ , l = 7.5, m = 90.5, n = 2.0)
* 2: Marcote 295 (Lubrizol Advanced Materials, Inc., charge density 6.0 meq / g)
* 3: BY11-003 (Toray Dow Corning)
* 4: Cosmall 168M (Nisshin Oil Company)

Formulation Example 3 (hair gel) (mass%)
Itaconic acid-modified polyvinyl alcohol ^{* 1} 4.0
Dimethyldiallylammonium chloride / acrylic acid copolymer liquid (40% by mass) ^{* 2} 6.0
Ethanol 10.0
Glycerin 2.0
Dipropylene glycol 2.0
Benzyl alcohol 0.5
PEG-60 hydrogenated castor oil 0.3
(C12-14) s-Palace-9 1.0
Stearyltrimethylammonium chloride 0.25
Hydroxyethyl cellulose 2.0
Diethylaminohydroxybenzoyl hexyl benzoate ^{* 3} 0.01
Sodium chloride 1.0
Fragrance 0.05
pH adjuster (caustic potassium) Amount of pH 5.0
Purified water Total remaining 100
* 1: Itaconic acid modified polyvinyl alcohol (manufactured by Kuraray Co., Ltd., viscosity of 5.0 mPa · s at 4 ° C. in a 4 mass% aqueous solution, R ¹ = −H, R ² = −COO ⁻ , R ³ = − in the formula (1) CH ₂ COO ⁻ , l = 7.5, m = 90.5, n = 2.0)
* 2: Marcote 295 (Lubrizol Advanced Materials, Inc., charge density 6.0 meq / g)
* 3: Yubinar A PLUS (BASF)

Formulation Example 4 (Aerosol Foam) (mass%)
<Undiluted solution>
Maleic acid-modified polyvinyl alcohol ^{* 1} 2.0
Dimethyldiallylammonium chloride / acrylic acid copolymer liquid (40% by mass) ^{* 2} 3.13
Ethanol 4.5
Glycerin 1.0
Dipropylene glycol 2.0
Benzyl alcohol 0.2
(C12-14) s-Palace-9 1.0
Polyoxyethylene lauryl ether (16E.O.) 1.0
Stearyltrimethylammonium chloride 0.25
Diethylaminohydroxybenzoyl hexyl benzoate ^{* 3} 0.01
Fragrance 0.05
pH adjuster (caustic potassium) Amount of pH 5.0
Purified water Total remaining 100
* 1: Maleic acid-modified polyvinyl alcohol (manufactured by Kuraray Co., Ltd., viscosity of 5.0 mPa · s at 20 ° C. in a 4 mass% aqueous solution, R ¹ = —COO ⁻ , R ² = —COO ⁻ , R ³ = -H, l = 7.5, m = 90.5, n = 2.0)
* 2: Marcote 295 (Lubrizol Advanced Materials, Inc., charge density 6.0 meq / g)
* 3: Yubinar A PLUS (BASF)
<Propellant>
LPG (0.44MPa)
<Stock solution / propellant ratio>
93.0 / 7.0

Formulation Example 5 (Non-Aerosol Former) (mass%)
Itaconic acid-modified polyvinyl alcohol ^{* 1} 1.43
Diallyldimethylammonium chloride / acrylic acid copolymer liquid (40% by mass) ^{* 2} 2.5
Ethanol 11.0
Dipropylene glycol 2.0
Benzyl alcohol 0.2
Polysilicone-9 2.0
PEG-32 1.0
PEG-400 1.0
(C12-14) s-Palace-9 1.0
Stearyltrimethylammonium chloride 0.25
PEG-60 hydrogenated castor oil 0.3
PPG-10 Sorbitol 1.0
Setes-20 0.5
Diethylaminohydroxybenzoyl hexyl benzoate ^{* 3} 0.01
Fragrance 0.05
pH adjuster (caustic potassium) Amount of pH 5.0
Purified water Total remaining 100
* 1: Itaconic acid-modified polyvinyl alcohol (manufactured by Kuraray Co., Ltd., viscosity of 5.0 mPa · s at 4 ° C. in a 4% by weight aqueous solution, in formula (1), R ¹ = −H, R ² = −COO ⁻ , R ³ = − CH ₂ COO ⁻ , l = 7.5, m = 90.5, n = 2.0)
* 2: Marcote 295 (Lubrizol Advanced Materials, Inc., charge density 6.0 meq / g)
* 3: Yubinar A PLUS (BASF)

Formulation Example 6 (two-component hair dye) first agent: second agent = 1: 1 (mass ratio)
・ First agent (cream) (mass%)
Strong ammonia water (28% by mass) 1.5
Monoethanolamine 3.0
Ammonium bicarbonate 0.5
Dimethyldiallylammonium chloride / acrylic acid copolymer liquid (40% by mass) ^{* 1} 6.8
Amodimethicone (40% emulsion) ^{* 2} 1.0
Highly polymerized dimethylpolysiloxane (number average degree of polymerization 2700) 1.5
Dimethylpolysiloxane (number average degree of polymerization 550) 4.0
Cetostearyl alcohol 7.0
Octyldodecanol 1.0
Polyoxyethylene (40) cetyl ether 2.0
Polyoxyethylene (2) cetyl ether 1.0
Stearyltrimethylammonium chloride solution (28% by mass) 3.0
Dialkyl chloride (12-18) dimethylammonium solution (75% by mass) 0.5
Propylene glycol 3.0
Edetate tetrasodium 0.1
Ascorbic acid 0.3
Sodium sulfite 0.5
Paraphenylenediamine 0.4
Toluene-2,5-diamine 0.4
Paraaminophenol 0.5
Metaaminophenol 0.2
2-Methyl-5-aminophenol 0.1
Resorcin 0.4
Fragrance 0.5
Purified water Total remaining 100
* 1: Marcote 295 (Lubrizol Advanced Materials, Inc., charge density 6.0 meq / g)
* 2: Silicone SM8704C (Toray Dow Corning Silicone)

・ Second agent (cream) (mass%)
Hydrogen peroxide solution (35% by mass) 16.2
8-quinolinol sulfate 0.04
Polyoxyethylene (40) cetyl ether 1.0
Polyoxyethylene (2) cetyl ether 1.0
Itaconic acid-modified polyvinyl alcohol ^{* 3} 3.6
Cetostearyl alcohol 3.5
Amount to make phosphoric acid pH 3.5
Purified water Total remaining 100
* 3: Itaconic acid modified polyvinyl alcohol (manufactured by Kuraray Co., Ltd., viscosity of 5.0 mPa · s at 20 ° C. in 4% by weight aqueous solution, R ¹ = −H, R ² = −COO ⁻ , R ³ = − in the formula (1) CH ₂ COO ⁻ , l = 7.5, m = 90.5, n = 2.0)

Formulation Example 7 (two-component hair dye) first agent: second agent = 1: 1 (mass ratio), gel after mixing, first agent (gel) (mass%)
Strong ammonia water (28% by mass) 5.0
Polydimethylmethylenepiperidinium chloride liquid (40% by mass) ^{* 1} 6.8
Oleic acid 5.0
Octyldodecanol 1.0
Polyoxyethylene (10) nonylphenyl ether 20.0
Polyethylene glycol 20.0
Sodium sulfite 0.5
Paraphenylenediamine 2.0
Orthoaminophenol 0.5
Resorcin 0.5
Fragrance 0.1
Purified water Total remaining 100
* 1: Marcote 100 (Lubrizol Advanced Materials, Inc., charge density 6.2 meq / g)

Second agent (liquid) (mass%)
Hydrogen peroxide solution (35% by mass) 15.0
Edetate tetrasodium 0.5
Cetanol 2.0
Sodium lauryl sulfate 0.5
Itaconic acid-modified polyvinyl alcohol ^{* 2} 3.6
Phenacetin 0.1
Purified water Total remaining 100
* 2: Itaconic acid modified polyvinyl alcohol (manufactured by Kuraray Co., Ltd., viscosity of 5.0 mPa · s at 20 ° C. in 4% by weight aqueous solution, R ¹ = −H, R ² = −COO ⁻ , R ³ = − in the formula (1) CH ₂ COO ⁻ , l = 7.5, m = 90.5, n = 2.0)

Formulation Example 8 (acid hair dye) (mass%)
Black 401 No.0.2
Purple 401 0.3
Yellow No.4 0.3
Benzyl alcohol 4.0
Citric acid 0.3
Dimethyldiallylammonium chloride / acrylic acid copolymer liquid (40% by mass) ^{* 1} 3.4
Itaconic acid-modified polyvinyl alcohol ^{* 2} 1.8
N-stearoyl-N-methyltaurine sodium 20.0
Stearyl alcohol 8.0
Dimethylpolysiloxane (6cs) 2.0
Dimethylpolysiloxane emulsion polymer 2.0
Fragrance 0.1
Purified water Total remaining 100
* 1: Marcote 295 (Lubrizol Advanced Materials, Inc., charge density 6.0 meq / g)
* 2: Itaconic acid modified polyvinyl alcohol (manufactured by Kuraray Co., Ltd., viscosity of 5.0 mPa · s at 20 ° C. in 4% by weight aqueous solution, R ¹ = −H, R ² = −COO ⁻ , R ³ = − in the formula (1) CH ₂ COO ⁻ , l = 7.5, m = 90.5, n = 2.0)

Formulation Example 9 (Color Rinse Containing Acid Dye) (mass%)
Black 401 No. 0.03
Purple 401 0.01
Yellow No. 0.01
Benzyl alcohol 3.0
Dipropylene glycol 15.0
Citric acid 1.5
Polydimethylmethylenepiperidinium chloride solution (40% by mass) ^{* 1} 3.4
Itaconic acid-modified polyvinyl alcohol ^{* 2} 1.8
Methylphenylpolysiloxane 4.0
Polyoxyethylene hydrogenated castor oil EO40 1.0
Hydroxyethyl cellulose 2.5
Purified water Total remaining 100
* 1: Marcote 100 (Lubrizol Advanced Materials, Inc., charge density 6.2 meq / g)
* 2: Itaconic acid modified polyvinyl alcohol (manufactured by Kuraray Co., Ltd., viscosity of 5.0 mPa · s at 20 ° C. in 4% by weight aqueous solution, R ¹ = −H, R ² = −COO ⁻ , R ³ = − in the formula (1) CH ₂ COO ⁻ , l = 7.5, m = 90.5, n = 2.0)

Formulation Example 10 (Color rinse containing basic dye) (mass%)
Cetyltrimethylammonium chloride 1.00
Cetostearyl alcohol 2.75
Coconut monoethanolamide 1.00
Paraffin wax 1.00
Basic Blue 99 0.15
Dimethyldiallylammonium chloride / acrylic acid copolymer liquid (40% by mass) ^{* 1} 3.4
Itaconic acid-modified polyvinyl alcohol ^{* 2} 1.8
Basic Brown 16 0.03
HC Blue 2 0.15
Disperse Violet 4 0.20
Fragrance 0.70
Preservative 0.25
pH adjuster
Purified water Total remaining 100
* 1: Marcote 100 (Lubrizol Advanced Materials, Inc., charge density 6.2 meq / g)
* 2: Itaconic acid modified polyvinyl alcohol (manufactured by Kuraray Co., Ltd., viscosity of 5.0 mPa · s at 20 ° C. in 4% by weight aqueous solution, R ¹ = −H, R ² = −COO ⁻ , R ³ = − in the formula (1) CH ₂ COO ⁻ , l = 7.5, m = 90.5, n = 2.0)

Claims (7)

A hair cosmetic comprising the following components (A) and (B):
(A) Cationic polymer having a charge density of 5.0 meq / g or more and 7.0 meq / g or less
(B) Anionic polymer represented by the general formula (1) and having a viscosity of 4.0 to 40.0 mPa · s at 20 ° C. in a 4% by mass aqueous solution

[In the formula, at least one of R ¹ and R ² represents —COO ⁻ , and the remainder represents a hydrogen atom, R ³ represents a hydrogen atom or —CH ₂ COO ⁻ , provided that ^one of R ¹ and R ² represents hydrogen. when an atom is R ³ is -CH ₂ COO ^- in and, l is 1.3 to 10, m + n is 90 or more 98.7 or less, l + n + m represents the 100. ]   The hair cosmetic composition according to claim 1, wherein the component (A) is at least one selected from the group consisting of a polymer containing a diallyl quaternary ammonium salt as a structural unit and a quaternized polyvinyl imidazolium derivative.   The hair cosmetic according to claim 2, wherein the polymer containing a diallyl quaternary ammonium salt as a constituent unit is a homopolymer of diallyl quaternary ammonium salt or a copolymer of diallyl quaternary ammonium salt and acrylic acid.   Hair cosmetics in any one of Claims 1-3 whose content of a component (A) is 0.01 mass% or more and 20 mass% or less.   Hair cosmetics in any one of Claims 1-4 whose content of a component (B) is 0.01 mass% or more and 20 mass% or less.   The hair cosmetic composition according to any one of claims 1 to 5, wherein the mass ratio (A) / (B) of the component (A) to the component (B) is 0.1 or more and 30 or less.   The hair cosmetic composition according to any one of claims 1 to 6, wherein the charge density of component (A) is from 5.5 meq / g to 6.5 meq / g.